Water-Free Rare Earth-Prussian Blue Type Analogues: Synthesis, Structure, Computational Analysis, and Magnetic Data of {LnIII(DMF)6FeIII(CN)6}∞
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- 作者：Duane C. Wilson ; Shengming Liu ; Xuenian Chen ; Edward A. Meyers ; Xiaoguang Bao ; Andrey V. Prosvirin ; Kim R. Dunbar ; Christopher M. Hadad ; Sheldon G. Shore
- 刊名：Inorganic Chemistry
- 出版年：2009
- 出版时间：July 6, 2009
- 年：2009
- 卷：48
- 期：13
- 页码：5725-5735
- 全文大小：1018K
- 年卷期：v.48,no.13(July 6, 2009)
- ISSN：1520-510X
文摘
Water-free rare earth(III) hexacyanoferrate(III) complexes, {Ln(DMF)6(μ-CN)2Fe(CN)4}∞ (DMF = N,N-dimethylformamide; Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Ho, 6; Er, 7; Tm, 8; Yb, 9; Lu, 10; Y, 11; La, 12; Ce, 13; Pr, 14; Nd, 15), were synthesized in dry DMF through the metathesis reactions of [(18-crown-6)K]3Fe(CN)6 with LnX3(DMF)n (X = Cl or NO3). Anhydrous DMF solutions of LnX3(DMF)n were prepared at room temperature from LnCl3 or LnX3·nH2O under a dynamic vacuum. All compounds were characterized by IR, X-ray powder diffraction (except for 10), and single crystal X-ray diffraction (except for 2, 7, 10). Infrared spectra reveal that a monotonic, linear relationship exists between the ionic radius of the lanthanide and the νμ-CN stretching frequency of 1−10, 12−15 while 11 deviates slightly from the ionic radius relationship. X-ray powder diffraction data are in agreement with powder patterns calculated from single crystal X-ray diffraction results, a useful alternative for bulk sample confirmation when elemental analysis data are difficult to obtain. Eight-coordinate Ln(III) metal centers are observed for all structures. trans-cyanide units of [Fe(CN)6]3− formed isocyanide linkages to Ln(III) resulting in one-dimensional polymeric chains. Structures of compounds 1−9 and 11 are isomorphous, crystallizing in the space group C2/c. Structures of compounds 12−15 are also isomorphous, crystallizing in the space group P2/n. One unique polymeric chain exists in the structures of 1−9 and 11 while two unique polymeric chains exist in structures of 12−15. One of the polymeric chains of 12−15 is similar to that observed for 1−9, 11 while the other is more distorted and has a shorter Ln-Fe distance. Magnetic susceptibility measurements for compounds 3−6, 8, 11 were performed on polycrystalline samples of the compounds.